Polycyclic diols and process for preparing the same

ABSTRACT

4 - HYDROXY-1-METHYLOL-6-OXA (3.2.1)-BICYCLO-OCTANE, 4HYDROXY - 1 - METHYLOL-6-OXA (3.2.1.1**3,8)-TRICYCLO-NONANE, AND 4-HYDROXY-1-METHYLOL-6,8-DIOXA (3.2.1-BICYCLO-OCTANE ARE PREPARED BY REACTING IN THE PRESENCE OF A CATALYST SUCH AS TUNGSTIC ACID, A PERACID WITH A CYCLIC DIOL SUCH AS 1,1DIMETHYLOL - 3-CYCLOHEXENE, 2,2-DIMETHYLOL-5-NORBORNENE, 2,2-DIMETHYLOL-3,4-DIHYDRO (2H) PYRANE. THE PERACID MAY BE PREPARED IN SITU BY REACTING HYDROGEN PEROXIDE WITH A CARBOXYLIC ACID.

United States Patent 3,654,311 POLYCYCLIC DIOLS AND PROCESS FORPREPARING THE SAME Arsene Isard, St. Genis, Laval, and Francis Weiss,Pierre Benite, France, assignors to Ugine Kuhlmann, Paris, France NoDrawing. Original application Jan. 4, 1968, Ser. No. 695,572. Dividedand this application May 25, 1970, Ser. No. 48,682 Claims priority,applicatitlrgtFrance, Jan. 6, 1967,

Int. Cl. 607a 13/04 US. Cl. 260-3403 1 Claim ABSTRACT OF THE DISCLOSURE4 hydroxy-l-methylol-6-oxa (3.2.1)-bicyclo-octane, 4- hydroxy 1methylol-6-oxa (3.2.1.1 )-tricyc1o-nonane, and4-hydroxy-1-methy1ol-6,8-dioxa (3.2.1 -bicyclo-octane are prepared byreacting in the presence of a catalyst such as tungstic acid, a peracidwith a cyclic diol such as 1,1- dimethylol 3-cyclohexene,2,2-dimethylol--norbornene, 2,2-dimethylol-3,4-dihydro (2H) pyrane. Theperacid may be prepared in situ by reacting hydrogen peroxide with acarboxylic acid.

This application is a division of my application Ser. No. 695,572, filedJan. 4, 1968.

FIELD OF THE INVENTION This invention relates to polycyclic diols andthe method for preparing the same.

SUMMARY OF THE INVENTION Polycyclic diols of the formula 0---0H2 whereinR is a hydrogen atom, X is the group CHR'- or an oxygen atom in which Ris a hydrogen atom or together with R forms a methylene bridge --CH isprepared by reacting an epoxydation or a hydroxylation agent such as acarboxylic peracid or an inorganic peracid with a cyclic diol of theformula CHR CH CH2 CHzOH \X/ omorr wherein R and X each has the samemeaning as defined hereinabove. The suitable unsaturated cyclic diolsare 1,1- dimethylol 3-cyclohexene, 2,2-dimethylol-5-norbornene, and2-2-dimethylol-3,4-dihydro (2H) pyrane.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Patented Apr. 4, 1972metachloroperbenzoic acid, monopermaleic acid, monoperphthalic acid. Thepreferred inorganic acid includes persulfuric acid and Caros acid.

Advantageously, the carboxylic peracid used in the reaction may beprepared in situ by adding hydrogen peroxide to a reaction mixturecontaining a suitable carboxylic acid such as formic acid or aceticacid, or a diacid anhydride such as maleic anhydride or phthalicanhydride, and the unsaturated cyclic diol. The preferred processcomprises treating the diol with hydrogen peroxide in an aqueous mediumat a temperature in the range between 30 and 70 C., and in the presenceof an inorganic catalyst such as osmium tetroxide, tungstic acid, acidsodium tungstate, molybdic acid. In this preferred form of the process,the required amount of hydrogen peroxide, which may be in the form ofcommercial peroxides containing 30% to by weight of H 0 in an aqueoussolution, and is used in the range between 1 to 1.5 mol of H 0 per molof the cyclic diol, is added to a solution of the cyclic diol in thepresence of the suitable catalyst, and the reaction is allowed to reactto completion. Thereafter the catalyst is removed by filtration and theexcess solvent in the filtrate is evaporated. The polycyclic diol ofthis invention is recovered by either distilling under produced pressureor by crystallization. The solution of the cyclic diol preferably iswater or an aqueous mixture containing inert water miscible inertsolvent such as methyl alcohol, ethyl alcohol, isopropanol and dioxane.

The temperature for the reaction may be varied within the range of 30 toC. Preferably it is maintained substantially in the same temperaturebetween 50 and 80 C. It is also possible to react at a temperature inthe range between 30 to 70 C. at the first part of the reaction andthereafter allowing the temperature to reach to the temperature in therange between 70 C. and the boiling point of the reaction mixture.

The amount of catalyst that may be used to promote the reaction whenhydrogen peroxide is used may vary within a wide range. In general, theamount required is within the limit of from trace amount to about 20 molpercent of the cyclic diol used in the reaction. Using tungstic acid,for example, the optimum quantity of catalyst is of about 1 to 10 molpercent of the cyclic diol.

The concentration of the cyclic diol in the reaction medium is notcritical; it is generally limited by its solubility in the reactionmedium, particularly if water is used alone. It is, however, notessential that all the cyclic diol is dissolved in the reaction mediumat the start of the reaction. The dissolution may be continuous duringthe reaction. We prefer to use about 2 to 20 parts by weight of solventper part of the cyclic diol to prepare the reaction solution.

The polycyclic diols of this invention may be used as hygroscopicagents, as solvents or dispersion agents for pigments, as startingmaterials for the production of polyesters or polyurethanes, for theproduction of paints and synthetic fibers.

Further to illustrate this invention, specific examples are describedhereinbelow.

Example 1.Production of 4-hydroxy l-methylol 6-oxa bicyclo 3.2. 1 octaneCH2 HO-CH CH2 H (Lemon g g. of water at 60 C., after which 40 g. ofaqueous solution at 34% by Weight of hydrogen peroxide (being 0.4 mol ofH was added in minutes. The mixture was stirred for an hour at the sametemperature. Additional 10 g. of solution at 34% of H 0 (0.1 mol) wasadded to the solution and the temperature was maintained at 60 C. foranother hour, after which the mixture was brought to boiling point for30 minutes. After cooling, the catalyst was filtered, and the filtratewas concentrated by evaporation of the water under the vacuum of a watersiphon. Distillation was performed finally under a pressure of about 1mm. of mercury. 43 g. 4-hydroxy l-methylol 6-oxa bicyclo (3.2.1) octane(0.27 mol) was obtained, to provide a yield of 67.5% based on thedimethylol-cyclohexene used.

The product is a very viscous colorless liquid having Bp =146153 C. andn =1.51O, and is very soluble in water.

Analysis by acetylation with acetic anhydride indicated an OH equivalentof 1.21 per 100 g., for a theoretical value of 1.26. This productyielded a crystallized p-nitrobenzole di-ester, melting at 147-148 C.,containing 6.14% of nitrogen (theoretical 6.14) and a crystallized3,5-dinitrobenzoic diester, melting at 200-201 C., containing 9.96% ofnitrogen (theoretical 10.25).

Example 2.Production of 4-hydroxy l-methylol 6-oxatricyclo (3.2.1.1nonane 77 g. of 2,2-dimethylol S-norbornene (0.5 mol) and 2.5 g. oftungstic acid (0.01 mol) were dissolved in 500 g. of water at 55 C.,after which 70 g. of aqueous solution at 34% by weight of hydrogenperoxide (0.7 mol of H 0 was added in 35 minutes. Thereafter the mixturewas maintained at the same temperature for half an hour before it wasraised to the boiling point of the mixture for another half an hour.After it was cool, the catalyst was filtered, and the excess Water wasevaporated by heating under the vacuum of a water siphon. The reactionproduct after concentration was distilled under a pressure of 0.5 to 1mm. of mercury. 64 g. distilled at 150 C., which largely crystallized atambient temperature, was recovered consisting of approximately 82% of4-hydroxy l-methylol 6-oxa tricyclo (3.2.1.1 nonane (52.5 g. =0.31 mol,or a yield of 62% based on the amount of cyclic diol used), 14% of theunconverted 2,2-dimethy'lol-S-norbornene, and traces of1methylol-G-oxa-tricyclo (3.2.1.1 nonane.

8 g. of a non-distillable residue remained which was very soluble inwater. The residue was probably a mixture of the normally expectedtetrol, 5,6-dihydroxy 2,2-dimethylol norbornane, and hydroxylatedpolycondensation products.

The distillate was treated with 200 g. of a mixture of benzenes andacetone, in the hot condition, to purify the reaction product. Acolorless crystalline precipitate was obtained by cooling, which wasfiltered, washed with cold benzene and dried. The dry weight was 46 g.This was pure 4 hydroxy 1-methylol 6-oxa tricyclo (3.2.1.1 nonane(purity verified by liquid chromatography in an attenuated layer) in theform of crystals melting at 92- 93 C.

Analyses.--1.14 OH/100 g. (theoretical: 1.175) was determined byacetylation. The bis (3,5-dinitrobenzoic) ester, crystals melting at211-212" 0., contained 9.80% of nitrogen (theoretical 10.03).

We claim:

1. 4-hydroxy-1 methylol 6,8 dioxa (3.2.1)-bicycleoctane.

References Cited UNITED STATES PATENTS 3,047,586 7/1962 Dunlop et al.260340.9

ALEX MAZEL, Primary Examiner J. H. TURN'IPSEED, Assistant Examiner US.Cl. X.R.

(2)33 UN l'll'll) S'.l'1\.'l.l'l5 PA'J'I'IN'I' 0 F1 1 CI) CER'IIFICATEOF CORRECTION Dam April 4', 1972 Patent No. 3,654,311

law a FRANCIS WEISS and ARSENE LSARD It is certified that error appearsin the above-identified patent; and that: said Letters Patent are herebycorrected as shown below:

Column 2', line 24, "under produced pressure" should read -underreduced'pres'sure Column 3, lines 21-22 "p-nitrobenzole" shou1d read'-pnitrobenzoic- Signed and sealed this 18th day of July 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Atte sting Officer Commissionerof Patents

